EP1541707B1 - VERFAHREN ZUR HERSTELLUNG EINES ALUMINIUMOXID- ÜberzugS MIT KRISTALLSTRUKTUR VOM a-TYP ALS PRIMÄRSTRUKTUR - Google Patents

VERFAHREN ZUR HERSTELLUNG EINES ALUMINIUMOXID- ÜberzugS MIT KRISTALLSTRUKTUR VOM a-TYP ALS PRIMÄRSTRUKTUR Download PDF

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EP1541707B1
EP1541707B1 EP03784599A EP03784599A EP1541707B1 EP 1541707 B1 EP1541707 B1 EP 1541707B1 EP 03784599 A EP03784599 A EP 03784599A EP 03784599 A EP03784599 A EP 03784599A EP 1541707 B1 EP1541707 B1 EP 1541707B1
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Prior art keywords
film formation
alumina
crystal structure
film
films
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English (en)
French (fr)
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EP1541707A1 (de
EP1541707A4 (de
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Toshimitsu c/o Takasago Works in KK Kohara
Hiroshi c/o Takasago Works in KK Tamagaki
Yoshimitsu c/o Takasago Works in KK Ikari
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Kobe Steel Ltd
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Kobe Steel Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0073—Reactive sputtering by exposing the substrates to reactive gases intermittently
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3492—Variation of parameters during sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32733—Means for moving the material to be treated
    • H01J37/32752—Means for moving the material to be treated for moving the material across the discharge

Definitions

  • This invention relates to a method of producing ⁇ crystal structure-based alumina films and, more particularly, to a useful method by which ⁇ crystal structure-based alumina films for coating/covering wear-resistant members, such as cutting tools, sliding members and molds, can be formed efficiently.
  • the present invention also relates to a method of producing useful a crystal structure-based alumina films by which method the above-mentioned alumina films can be formed efficiently in a relatively low temperature range.
  • cutting tools and sliding members which are required to have good wear resistance and sliding characteristics, are used in the form having a hard coat film of titanium nitride, titanium aluminum nitride or the like as formed on the surface of a substrate such as a high speed steel or cemented carbide by the physical vapor deposition method (hereinafter referred to as "PVD method”) or chemical vapor deposition method (hereinafter referred to as "CVD method”), among others.
  • PVD method physical vapor deposition method
  • CVD method chemical vapor deposition method
  • the hard coat film mentioned above is required to have wear resistance and heat resistance (antioxidant properties at elevated temperatures), and the above-mentioned titanium aluminum nitride (TiAlN), for instance, which can retain both the characteristics mentioned above stably up to such a high temperature as about 800°C, has recently been in wide use as a coating/covering material for cemented carbide tools and the like the tip temperature of which becomes high on the occasion of cutting.
  • TiAlN titanium aluminum nitride
  • the tip of a cutting tool or the like may reach such a high temperature as 1,000°C or above in the step of cutting.
  • an alumina layer for example, is further formed after the formation of the above-mentioned hard coat film to secure heat resistance, as disclosed in Japanese Patent No. 2742049 .
  • the crystal structure of alumina varies depending on the formation temperature.
  • an amorphous structure predominates and, when it is within the range of about 500-1,000°C, the ⁇ crystal structure predominates.
  • either crystal structure is in a thermally metastable state.
  • the tip temperature varies markedly in a wide range of from ordinary temperature to 1,000°C or above in the step of cutting, as found with cutting tools, the crystal structure of alumina changes markedly, which causes problems, for example film cracking or/and peeling.
  • the ⁇ crystal structure (corundum structure), which is formed at a substrate temperature elevated to 1,000°C or above by employing the CVD method, once formed, preserves its thermally stable structure thereafter, irrespective of temperature. Therefore, coating with a crystal structure alumina is regarded as a very effective means for providing cutting tools or the like with heat resistance.
  • ⁇ crystal structure alumina cannot be formed without heating the substrate to 1,000°C or above, as mentioned above, there is a restriction as to applicable substrates.
  • some substrates When exposed to elevated temperatures exceeding 1,000°C, some substrates will be softened and lose their aptitude for use as substrates for wear-resistant members. Even such substrates for high temperature use as cemented carbides, when exposed to such high temperatures, cause problems such as deformation.
  • the temperature range for the practical use of hard coat films, such as TiAlN films, formed as wear resistance-providing films on substrates is generally about 800°C at the highest, so that when heated to high temperatures exceeding 1,000°C, the films may undergo denaturation, possibly leading to a deterioration in wear resistance.
  • JP-A-2002-53946 it is disclosed that the method comprising forming an ⁇ crystal structure alumina coat film on an undercoat layer of a corundum structure ( ⁇ crystal structure) oxide with a lattice parameter of not less than 4.779 ⁇ but not exceeding 5.000 ⁇ and a film thickness of at least 0.005 ⁇ m is effective.
  • the PVD method can readily form various compound layers under milder conditions as compared with the CVD method and, among others, the sputtering technique which comprises using a metal target as the sputtering evaporation source and forming a metal compound on a substrate in a reactive gas atmosphere is in wide use since it can form various kinds of compound layers more easily.
  • sputtering is carried out in an atmosphere of oxygen, which is a reactive gas, using an aluminum metal target to form alumina films on substrates.
  • the relation between the rate of flow of oxygen gas introduced and the discharge voltage is represented by such a hysteresis curve as schematically shown in Fig. 1 when the discharge power is constant. More specifically, when the oxygen flow rate is gradually increased from a low level, the discharge voltage rapidly decreases at a certain oxygen flow rate and, conversely, when the oxygen flow rate is gradually decreased from a high level, the discharge voltage rapidly increases at a certain oxygen flow rate, as shown in Fig. 1 .
  • Such discharge conditions mentioned above are generally classifiable into three modes, as schematically illustrated in Fig. 1 , namely the metal mode in which the discharge voltage is relatively high and the oxygen gas introduced is mostly consumed in alumina formation as a result of reaction with aluminum atoms formed by sputtering, the poisoning mode in which the discharge voltage is relatively low and the oxygen gas introduced still remains in excess after reaction with aluminum atoms formed by sputtering, hence the aluminum target surface, too, is oxidized, and the transition mode in which the discharge voltage shows an intermediate value between the above two discharge conditions.
  • One method comprises maintaining the oxygen flow rate at a substantially constant level and controlling the discharge voltage.
  • Fig. 2 shows the relation between the discharge voltage and discharge current as found in sputtering of an aluminum metal target while varying the voltage in an Ar gas and an oxygen gas (the rates of flow of both being constant).
  • the transition mode condition can be maintained almost stably by adequately controlling the discharge voltage.
  • JP-A-H04-325680 discloses that, when the dual magnetron sputtering (DMS) technique is employed for film formation, the discharge condition can be adjusted to the transition mode by controlling the oxygen gas flow rate so that the measured voltage of the sputtering cathode may be equal to the desired voltage. Further, in JP-A-H04-136165 , it is disclosed that the discharge condition can be stabilized and qualitatively stable films can be obtained by controlling the partial pressure of a reactive gas in the film-forming chamber, for example the partial pressure of oxygen.
  • DMS dual magnetron sputtering
  • the present invention has been made in view of such circumstances as discussed above, and it is an object of the invention to provide a method of producing useful a crystal structure-based alumina films by which ⁇ crystal structure-based alumina films having good heat resistance can be efficiently formed on substrates or hard coat films such as the above-mentioned TiAIN in a relatively low temperature range in which the substrates and apparatus, among others, will not be put under thermal load and by which ⁇ crystal structure-based alumina films higher in hardness can be formed on such substrates or hard coat films.
  • US 5698314 A discloses a vacuum deposition process, wherein at least one layer of material, having an outer layer of Al 2 O 3 , is applied to a carrier.
  • JP 2001-342556 layer discloses a method for manufacturing a thin film of ⁇ phase alumina.
  • the method of producing ⁇ crystal structure alumina films according to the invention is defined in claim 1 and comprises, as an initial film forming step, the step of forming alumina films under conditions suited for the formation of ⁇ crystal structure alumina in forming alumina films on substrates by sputtering of an aluminum metal target in an oxidizing gas-containing atmosphere (hereinafter sometimes referred to as "first mode of practice").
  • ⁇ crystal structure alumina films can favorably be formed with high efficiency.
  • the method comprising changing the discharge condition to the transition mode or metal mode and forming films after film formation in the poisoning mode discharge condition in the early stage of film formation, and the method comprising forming films at a film formation rate of not lower than 3 nm/min after film formation at a film formation rate of not higher than 1 nm/min in the early stage of film formation.
  • the method comprising lowering the substrate temperature to 650-750°C and forming films after film formation at a substrate temperature not lower than 800°C in the early stage of film formation.
  • films are formed by changing the conditions to those under which films with high hardness can be formed, as mentioned above, ⁇ crystal structure-based alumina films higher in hardness can favorably be obtained.
  • the method comprising forming films while applying no negative bias voltage to substrates or applying a relatively low bias voltage to substrates in the early stage of film formation and then forming films while applying a negative bias voltage or increasing the absolute value of that bias voltage, for example the method comprising forming films while applying a negative bias voltage not higher in absolute value than 100 V in the early stage of film formation and then forming films at a negative voltage increased to 200 V or above in absolute value.
  • the intermittent film formation cycles can properly controlled by adjusting the revolution speed of the turntable, satellite rotary members or rotary members.
  • the turntable is preferably rotated at 3 rpm or a greater revolution speed.
  • the satellite rotary members are rotated at 20 rpm or a greater revolution speed.
  • the intermittent film formation cycles can be controlled by appropriately adjusting the reciprocating cycle in the above-mentioned method (d), the shutter opening/closing cycle in the method (e), and the intermittent sputtering cycle in the method (f).
  • the present inventors made investigations in search of a method of efficiently forming ⁇ crystal structure-based alumina films (hereinafter sometimes referred to as " ⁇ type-based alumina films" for short) under reduced thermal load conditions relative to the substrates, hard coat films, apparatus and so forth by employing the method comprising sputtering an aluminum metal target(s) in an oxidizing gas-containing atmosphere.
  • ⁇ type-based alumina films for short
  • ⁇ type-based alumina films can be formed without fail even upon changing the film formation conditions in the middle and later stages of film formation to (i) those conditions suited for increasing productivity, (ii) those low temperature conditions suited for maintaining the characteristics of the substrates and so on, or (iii) those manufacturing conditions suited for the formation of alumina films higher in hardness and, as a result, a type-based alumina films can be efficiently formed at a high rate, or such films can be formed while suppressing the thermal load on the substrates, hard coat films already formed, apparatus and so forth, or a type-based alumina films higher in hardness can be obtained.
  • ⁇ crystal structure alumina formed in the early stage of film formation desirably has a thickness of at least about 1 nm.
  • ⁇ type-based alumina films are efficiently formed presumably because the ⁇ structure alumina crystal nuclei formed as an undercoat on the substrate in the early stage of film formation allow the subsequent growth of ⁇ crystal structure alumina with the ⁇ structure crystal nuclei already formed serving as bases therefor even if the production conditions are more or less changed thereafter.
  • the present inventors attempted alumina film formation on Cr 2 O 3 films in the poisoning mode discharge condition based on the known technology mentioned hereinabove.
  • ⁇ type-based alumina is indeed formed but the film formation rate is extremely slow, hence impractical.
  • film formation is carried out in the transition mode or metal mode discharge condition for increasing the film formation rate, the alumina films formed substantially show the ⁇ type crystal structure alone or an ⁇ type/ ⁇ type mixed crystal structure rich in ⁇ type; those films which the present invention is to provide cannot be obtained.
  • the present inventors investigated the relation between the discharge condition during film formation and the crystal structure of the alumina films formed, and found that when ⁇ crystal structure alumina is formed as an undercoat by carrying out the early stage of film formation alone in the poisoning mode, ⁇ type-based alumina films can be formed without fail even if the discharge condition is changed to the transition mode or metal mode in the middle and later stages of film formation for higher rate film formation.
  • the early film formation stage alone is carried out in the poisoning mode and, in the middle and later stage of film formation, the discharge condition is changed to the transition mode or metal mode in which the film formation rate is higher, with the result that the total film formation time is markedly shortened.
  • ⁇ crystal structure alumina when film formation is carried out in the transition mode discharge condition from the early stage of film formation, it is difficult to form ⁇ crystal structure alumina unless the substrate temperature is raised to about 800°C or above. It was found that when alumina films are formed by the method (I-1) mentioned above, ⁇ crystal structure alumina can be formed without fail and the thermal load on the substrates, apparatus and so forth can be reduced by controlling the substrate temperature in the middle and later stages of film formation so that it may not become lower than 700°C.
  • film formation in the metal mode readily allows contamination of alumina films with metallic aluminum, as mentioned hereinabove, film formation in the middle and later stages of film formation is preferably carried out in the transition mode discharge condition.
  • ⁇ crystal structure alumina was formed without fail by film formation at a film formation rate of not higher than 1 nm/min in the early stage of film formation alone and then film formation was carried out at an increased film formation rate of 3 nm/min or above, whereupon pure ⁇ crystal structure alumina films could be obtained almost in the same manner as the case in which film formation is carried out at a low rate not exceeding 1 nm/min throughout the film formation.
  • ⁇ structure alumina crystal nuclei are formed as an undercoat in the early stage of film formation, ⁇ crystal structure alumina can grow subsequently utilizing, as bases, the ⁇ structure crystal nuclei already formed when film formation is continued after changing the film formation conditions to those for higher rate film formation under which ⁇ crystal structure alumina is formed with difficulty.
  • the film formation rate in the early stage of film formation is not higher than 0.5 nm/min, ⁇ crystal structure alumina, which is to serve as an undercoat, can be formed without fail. Further, a film formation rate of not lower than 10 nm/min in the middle and later stages of film formation is desirable, since the film formation can then be accomplished with better efficiency.
  • the discharge condition in carrying out the method (I-2) is not particularly restricted but, for efficient film formation, the transition mode or metal mode is preferably employed and, as mentioned above, film formation in the transition mode is desirable for forming alumina films with a metal aluminum content as low as possible.
  • ⁇ structure alumina crystal nuclei are formed as an undercoat in the early stage of film formation, ⁇ crystal structure alumina can subsequently grow utilizing, as bases, the ⁇ structure crystal nuclei already formed even when the film formation conditions are changed to those unfavorable for the formation of ⁇ crystal structure alumina by lowering the substrate temperature.
  • the early stage of film formation is preferably carried out at a substrate temperature not lower than 800°C, more preferably 850°C or higher, since ⁇ type-based alumina can then be formed without fail.
  • the upper limit to the substrate temperature should be lower than 1,000°C.
  • ⁇ crystal structure alumina when ⁇ crystal structure alumina is formed in the early stage of film formation, a crystal structure alumina films can be obtained without fail even if the substrate temperature is lowered to about 650-750°C in the middle and later stages of film formation; the thermal load on the substrates and hard coat films already formed and, further, apparatus and so forth can be reduced, and the heating mechanisms can also be more simplified.
  • the film formation temperature in the middle and later stages of film formation is excessively low, the proportion of ⁇ crystal structure alumina increases, hence the substrate temperature is preferably not lower than 700°C.
  • the discharge condition to be selected in employing the method (II) is not particularly restricted, either, but the transition mode or metal mode is preferably employed for efficient film formation; for the same reasons as mentioned above, film formation in the transition mode is advantageous for the formation of alumina films with a metallic Al content as low as possible.
  • the present inventors investigated various film formation conditions to obtain ⁇ type-based alumina higher in hardness and found that the application of a negative bias voltage during film formation, in particular, is effective.
  • a negative bias voltage during film formation that is effective.
  • the films during film formation grow under bombardment with ions corresponding in energy to the bias voltage, with the results that the growing films become densified and/or the compression stress which the films have is increased.
  • the present inventors formed alumina films while applying a negative bias voltage of 300 V in absolute value throughout the whole film formation step and examined the films for hardness. Since alumina films are insulating films, the bias voltage was applied intermittently at a high frequency of 10 kHz or higher (in the following, including the examples, bias voltage application was carried out intermittently in this manner). The films obtained in the above manner had a high hardness of about 27 GPa. It was confirmed, however, by X ray diffraction analysis that the alumina films contained the ⁇ type crystal structure in small proportions.
  • the present inventors first formed a type-based alumina films by the above-mentioned method (I-1) without applying any bias voltage and then carried out film formation under the same constant conditions except that a negative bias voltage of 300 V in absolute value was applied to the substrates.
  • a negative bias voltage of 300 V in absolute value was applied to the substrates.
  • the hardness value was as high as about 26 GPa.
  • ⁇ structure alumina crystal nuclei are also formed as an undercoat in the early stage of film formation. Therefore, highly hard ⁇ crystal structure alumina can grow successively with the ⁇ structure crystal nuclei already formed serving as bases even when a negative bias voltage or a negative bias voltage increased in absolute value is later applied to thereby change the conditions to those favorable for the formation of ⁇ alumina.
  • the step of forming ⁇ crystal structure alumina in the early stage of film formation without applying any negative bias voltage or while controlling the negative bias voltage, when applied, so that any other crystal phases than the ⁇ crystal structure phase may not be formed, and the subsequent step comprising forming highly hard ⁇ alumina while applying a negative bias voltage or a negative bias voltage higher in absolute value should be included.
  • the negative bias voltage to be applied in forming ⁇ alumina in the early stage of film formation should preferably be not higher than 100 V in absolute value (inclusive of the case of no bias voltage application) and that the application of a negative bias voltage of not lower than 200 V in absolute value in the middle of film formation and thereafter is adequate for attaining high hardness levels.
  • ⁇ crystal structure alumina is to be formed in the early stage of film formation without applying any negative bias voltage or by controlling the negative bias voltage, if applied, so that any other crystal phases than the ⁇ crystal structure phase may not be formed; thereafter, highly hard ⁇ alumina can be formed while applying a negative bias voltage or a negative bias voltage higher in absolute value.
  • the discharge condition during film formation is not particularly restricted.
  • the method (III) may be combined with the above-mentioned methods (I) and (II).
  • highly hard ⁇ type-based alumina can be formed efficiently by employing the above method (I-1) to promote the growth of ⁇ alumina crystals in the poisoning mode without applying any bias voltage and then changing the discharge condition from the poisoning mode to the transition mode to secure the growth of ⁇ alumina crystals in the transition mode and thereafter applying a negative bias voltage while maintaining the same discharge condition (namely the transition mode).
  • the method provided by the present invention can be applied also to the cases where the discharge condition is controlled by every means, for example controlling the discharge condition by varying the discharge voltage, or controlling the discharge condition by controlling some other factor such as the oxygen flow rate, oxygen partial pressure, discharge power or discharge current, for instance.
  • the sputtering method applicable in carrying out the method of the invention there may be mentioned not only the pulsed DC sputtering method but also the high-frequency sputtering method, magnetron sputtering method, and ion beam sputtering method, among others.
  • the present inventors made investigations from various angles to produce ⁇ crystal structure-based alumina films efficiently and without fail at relatively low temperatures in forming crystalline alumina films on substrates by introducing oxygen.
  • the present inventors further found that the thickness of the film formed in each substep in carrying out the intermittent film formation exerts an important influence on the formation of a crystal structure-based alumina films.
  • the respective conditions specified for the formation of ⁇ crystal structure-based alumina films in accordance with the second mode of practice are described in detail.
  • the present inventors made such experiments as mentioned below by establishing the transition mode discharge condition in which alumina films can be formed at a relatively high rate in an oxidizing atmosphere containing oxygen gas together with Ar.
  • a substrate was disposed so as to face the direction of sputtering of an aluminum metal target and film formation was carried out by continuous sputtering in the direction of the substrate.
  • the crystal structure of the alumina films obtained mostly comprised the ⁇ type alone but the ⁇ crystal structure could not be confirmed.
  • a turntable 3 or the like was disposed so as to face the direction of sputtering of each aluminum metal target, as shown in Figs. 3 to 5 , which are to be described later herein, substrates were fixed to the turntable 3 or the like, and film formation was carried out intermittently while rotating the turntable 3 or the like. In that case, the formation of ⁇ crystal structure alumina could be confirmed.
  • the environment while the sputtering cathode and substrate are facing each other and an alumina film is formed on the substrate, is in the same condition as in continuous film formation during which the sputtering cathode and substrate stand still facing each other and an alumina film is formed on the substrate.
  • the film just formed is supposedly exposed to oxygen gas fed to the inside of the apparatus and oxygen is fed thereto.
  • the exposure to an oxygen excess atmosphere similar to that in the poisoning mode discharge condition exerts an effective influence on the formation of ⁇ crystal structure alumina.
  • the present inventors investigated the quantitative influence of the thickness of the film formed in each film formation substep on the crystal structure of the alumina film obtained, and found that, for forming ⁇ crystal structure-based alumina films, it is necessary for the film thickness obtained in each substep to be not greater than 5 nm.
  • the film thickness per substep exceeds 5 nm, the proportion of the ⁇ crystal structure increases and alumina films mainly having the ⁇ crystal structure can no longer obtained.
  • a presumable reason therefore is that when the film thickness per substep is excessive, oxygen supply to the films becomes insufficient during the substep involving no film formation.
  • the present inventors further found that even when the average film formation rate is identical, alumina films higher in ⁇ crystal structure percentage can be formed by reducing the film thickness per substep. It was confirmed that when the film thickness per substep is suppressed to 2 nm or less, the ⁇ crystal structure can occupy almost the whole area of the resulting alumina film while the ⁇ crystal structure exists only in slight amounts, and that when the film thickness per substep is reduced preferably to 1 nm or less, alumina films substantially having the ⁇ crystal structure alone can be formed.
  • the lower limit to the film thickness per substep is about 0.3 nm.
  • the present inventors made experiments in which the thickness of the film formed in each substep was varied between the early stage and the middle and later stages of film formation. As a result, it was revealed that when film formation is carried out while suppressing the film thickness per substep in the early stage of film formation to 2 nm or less, alumina films higher in a crystal structure content can be formed even if the film thickness per substep in the middle and later stages of film formation is increased within the range not exceeding 5 nm.
  • the method comprising increasing the film thickness per substep in the middle and later stages of film formation is desirable since the load on the apparatus, in particular the rotating mechanisms, which is to be described later herein, can be reduced. Further, in the case of production in such a manner, the film formation rate in the middle and later stages of film formation can be increased, and this is favorable from the viewpoint of increased film formation efficiency.
  • Figs. 3-5 there may be mentioned the method comprising fixing substrates to a turntable or the like disposed so as to face the direction of sputtering of each aluminum metal target and forming alumina films intermittently while rotating the substrates by rotating the turntable or the like.
  • each rotary member 8 disposed on each satellite rotary member 4 adds to the rotation and revolution resulting from the combination of the turntable 3 and each satellite rotary member 4, as shown in Fig. 4 , so that the film formation time per substep can be further shortened as compared with the example shown in Fig. 4 , hence the film thickness per substep can be extremely reduced.
  • the film thickness per substep can be controlled with ease by adjusting the revolution speed of the above-mentioned turntable 3, satellite rotary members 4, or rotary members 8.
  • the rotary table 3 is preferably rotated at 3 rpm or a greater revolution speed, more preferably at 6 rpm or a greater revolution speed.
  • the satellite rotary members 4 are preferably rotated at 20 rpm or a greater revolution speed, since, on that occasion, the film thickness per substep can be reduced and the formation of ⁇ crystal structure alumina becomes easier.
  • a more preferred revolution speed of the satellite rotary members 4 is 40 rpm or greater.
  • the apparatus shown in Figs. 3-5 are provided, on the wall surface, with two heaters 5 for heating substrates and so forth.
  • the wall surface may be provided with one or more additional heaters and, further, as shown in relation to the apparatus used in the examples to be mentioned later herein, a center heater may further be disposed approximately in the center of the turntable.
  • the radiant heat from the center heater is thought to activate the atoms in each alumina film just after formation thereof, so that the reaction with oxygen, among others, in the atmosphere may presumably be promoted in each period during which no film formation is carried out, hence crystallization may presumably be promoted in a favorable manner.
  • sputtering cathodes are disposed at two sites. Where necessary, film formation may be carried out using one sputtering cathode alone, or one or more further sputtering cathodes may be disposed so that sputtering may be realized at three or more sites.
  • the other film formation conditions to be employed in the practice of the invention are not particularly restricted.
  • To employ the transition mode as the discharge condition during sputtering is very effective in increasing the film formation rate and forming alumina films free of metallic aluminum, as mentioned above.
  • the transition mode discharge condition can be attained not only by controlling the discharge condition by varying the discharge voltage but also by controlling another factor or factors, such as the oxygen flow rate and/or oxygen partial pressure, discharge power, discharge current, etc.
  • the present invention not only aims at forming alumina films free of metallic aluminum but also is based on the assumption that film formation should be carried out in an oxidizing gas-containing atmosphere so that the oxygen exposure effect may be obtained during each film formation-free period, as mentioned above.
  • the oxygen partial pressure may be increased by feeding oxygen gas into the Ar atmosphere and, further, the method comprising feeding O 3 or H 2 O 2 to the Ar atmosphere may be mentioned.
  • the method of sputtering which can be applied in the practice of the invention includes the pulsed DC sputtering method and, further, the high-frequency sputtering method, magnetron sputtering method, and ion beam sputtering method, among others.
  • alumina film formation was carried out using a turntable and so forth in the examples given below relating to the second mode of practice, the present invention is not limited to such examples but of course includes the use of such a shutter mechanism as mentioned above or the use of the intermittent sputtering technique.
  • the CrN film oxidation and the ⁇ type-based alumina film formation were carried out in the following manner using a vacuum film forming apparatus equipped with magnetron sputtering cathodes, heaters, substrate rotating mechanisms and so forth [model AIP-S40 multiple function machine, product of Kobe Steel, Ltd.].
  • samples (CrN film-covered cemented carbide substrates) 2 were set on satellite rotary members (substrate holders) 4 on a turntable 3 in the apparatus 1, and the apparatus inside was evacuated almost to a vacuum condition and, then, the samples were heated to the substrate temperature for the early stage of film formation as specified in Table 1 by means of heaters 5. After attainment of the specified sample temperature, oxygen gas was introduced into the apparatus 1 and the CrN film on the sample surface was oxidized, and the resulting samples were used as substrates for ⁇ type-based alumina film formation.
  • Example 2 of the invention to be mentioned later herein discharge was carried out using one sputtering cathode 6 and, in other examples, two sputtering cathodes 6 were used.
  • the discharge power was about 2 to 3.2 kW per sputtering cathode 6. Only in the early stage of film formation in Example 3 of the invention to be mentioned later herein, the discharge power was about 300 W per sputtering cathode 6.
  • the Ar gas flow rate was maintained at a constant level of 120 sccm, the oxygen gas flow rate and discharge voltage were adequately adjusted to attain the specified discharge condition.
  • the gas evaporated was analyzed by a plasma emission spectrometer analyzer located at about 20 mm distant from the sputtering surface of the target, and the discharge voltage was adjusted using the emission intensities of aluminum and oxygen as measures to attain the specified discharge condition.
  • the film formation was carried out while rotating the turntable 3 and satellite rotary members (substrate holders) 4, as shown in Fig. 7 .
  • the discharge condition, the substrate temperature, the film formation times in the early stage and middle and later stages of film formation during film formation were as shown in Table 1.
  • the thicknesses of the thus-formed alumina films were determined by measuring the differences in level on a silicon substrate.
  • the alumina film surface was subjected to grazing incidence X ray diffraction analysis (grazing incidence XRD analysis) to identify the crystal structure.
  • the extent of the formation of ⁇ crystal structure alumina was estimated from the results of X ray diffraction analysis by examining the presence or absence of the peak indicating ⁇ crystal structure alumina and the peak indicating ⁇ crystal structure alumina. The results thus obtained are shown in Table 1, together with the film formation conditions.
  • Comparative Example 2 and Comparative Example 3 films were formed in the constant discharge condition, namely in the transition mode, and the substrate temperature in Comparative Example 2 was the same as that in Comparative Example 1, namely 750-780°C, and that in Comparative Example 3 was relatively low, namely 650-680°C. In each of Comparative Example 2 and Comparative Example 3, films were formed in the transition mode, so that the film formation could be realized at a rate about 10 times that in Comparative Example 1.
  • Example 1 of the invention the film formation was carried out in the poisoning mode in the early stage of film formation alone and the discharge condition was then changed to the transition mode for continued film formation.
  • the rate of film formation in Example 1 of the invention was significantly higher as compared with Comparative Example 1 mentioned above, namely almost the same as in Comparative Example 2 or 3 mentioned above. Unlike Comparative Examples 2 and 3, however, alumina films having the ⁇ crystal structure alone were obtained.
  • Example 2 of the invention the film formation was carried out in a lower temperature range throughout the whole film formation period as compared with Example 1 of the invention.
  • Example 1 of the invention results obtained in Example 1 of the invention and Example 2 of the invention indicate that when ⁇ alumina crystal nuclei are formed as an undercoat in the poisoning mode in the early stage of film formation, the ⁇ type is formed with ease even if the subsequent film formation is carried out in the transition mode.
  • Example 3 of the invention films were formed for 10 minutes at a film formation rate of about 0.5 nm/min and at a discharge power decreased by adjusting the oxygen flow rate and discharge voltage in the early stage of film formation alone, and the subsequent film formation was carried out at a film formation rate of about 5 nm/min while the discharge power was increased; the discharge condition throughout the whole film formation period was the transition mode.
  • Example 3 of the invention ⁇ crystal structure alumina is formed as an undercoat by film formation at a decrease rate of film formation in the early stage of film formation alone even when the film formation is carried out in the transition mode, and that even when the film formation rate is increased thereafter, ⁇ type-based alumina films can be formed.
  • Example 4 of the invention films were formed at an early film formation stage substrate temperature somewhat higher than that in Example 3 of the invention and the substrate temperature in the middle and later stages of film formation was in a lower temperature range than in Example 3 of the invention.
  • ⁇ alumina crystal nuclei were formed in the early stage of film formation at elevated temperatures, and ⁇ alumina was formed selectively and a type-based alumina films were formed in spite of the fact that the subsequent film formation was carried out at a lowered substrate temperature.
  • the CrN film oxidation and the ⁇ type-based alumina film formation were carried out in the following manner using a vacuum film forming apparatus equipped with magnetron sputtering cathodes, heaters, substrate rotating mechanisms and so forth [model AIP-S40 multiple function machine, product of Kobe Steel, Ltd.].
  • samples (CrN film-covered cemented carbide substrates) 2 were set on satellite rotary members (substrate holders) 4 on a turntable 3 in the apparatus 1, and the apparatus inside was evacuated almost to a vacuum condition and, then, the samples were heated to the substrate temperature of 750°C by the heaters 5. After attainment of the specified sample temperature, oxygen gas was introduced into the apparatus 1 and the CrN film on the sample surface was oxidized, and the resulting samples were used as substrates for ⁇ type-based alumina film formation.
  • ⁇ crystal structure-based alumina film was formed on the above-mentioned oxidized layer.
  • the alumina film formation was carried out in an argon-oxygen atmosphere by the pulsed DC sputtering method using two sputtering cathodes 6.
  • the discharge power was about 2 to 3.2 kW per sputtering cathode 6.
  • the Ar gas flow rate was maintained at a constant level of 120 sccm, the oxygen gas flow rate and discharge voltage were adequately adjusted to attain the specified discharge condition.
  • the gas evaporated was analyzed by a plasma emission spectrometer analyzer located at about 20 mm distant from the sputtering surface of the target, and the discharge voltage was adjusted using the emission intensities of aluminum and oxygen as measures to attain the specified discharge condition.
  • the film formation was carried out while rotating the turntable 3 and satellite rotary members (substrate holders) 4, as shown in Fig. 7 .
  • Comparative Example 11 to be compared with the above example films were formed in the same manner as in Example 1 of the invention in the above-mentioned Example 1.
  • the film formation was carried out in the poisoning mode discharge condition for 10 minutes while the substrate temperature was maintained at 750°C. Thereafter, the substrate temperature was maintained at the above-mentioned level, the discharge condition alone was changed to the transition mode, and the film formation was continued for 2 hours and 50 minutes.
  • the film formation was carried out without applying any bias voltage to the substrates.
  • the crystal structure of the films obtained was examined in the same manner as Examples 1 mentioned above by grazing incidence X ray diffraction and was confirmed to be of the ⁇ alumina single phase.
  • the film hardness confirmed by the nanoindentation method was 22 GPa.
  • the method of hardness measurement by the nanoindentation technique is as follows. After polishing the film surface, five loads differing in level from 30 to 200 mN were applied to the surface using an Elionix model "ENT-1100a" apparatus with a Berkovich indenter, and the load-indentation depth characteristics were measured. The film hardness was determined by making calculations for calibration with respect to the frame compliance and indentation depth using the method proposed by Sawa et al. in J. Mater. Res., 16, 2001, pp. 3084-3096 .
  • Comparative Example 12 films were formed while a negative bias voltage of 300 V in absolute value was applied throughout the whole film formation step in Comparative Example 11 mentioned above.
  • the hardness of the films obtained was checked by the above-mentioned nanoindentation method and found to be 27 GPa, namely a higher hardness as compared with Comparative Example 11 in which no bias voltage was applied.
  • the films were contaminated with ⁇ alumina although they were mainly of the ⁇ type.
  • Example 11 of the invention films were formed in the following manner. In the early stage of film formation, films were formed at a substrate temperature of 750°C for 10 minutes while the discharge condition was maintained in the poisoning mode and, then, the discharge condition was changed to the transition mode and film formation was continued for 30 minutes. The above step was carried out without applying any bias voltage. Thereafter, film formation was carried out for 2 hours and 20 minutes while a negative bias voltage of 300 V in absolute value was applied and the above-mentioned conditions were maintained. The total film formation time was 3 hours. The thickness of the alumina films obtained was about 1.8 ⁇ m.
  • Example 11 of the invention The crystal structure of the films obtained in Example 11 of the invention was checked by the grazing incidence X ray diffraction and found to be of the a crystal structure alumina single phase.
  • the hardness of the alumina films was measured by the above-mentioned nanoindentation method and found to be 26 GPa; thus, the films obtained were higher in hardness than those obtained in Comparative Example 11 in which no bias voltage was applied.
  • the CrN film oxidation and the ⁇ type-based alumina film formation were carried out in the following manner using a vacuum film forming apparatus equipped with magnetron sputtering cathodes, heaters, substrate rotating mechanisms and so forth [model AIP-S40 multiple function machine, product of Kobe Steel, Ltd.].
  • samples (CrN film-covered cemented carbide substrates) 2 were set on satellite rotary members (substrate holders) 4 disposed on a turntable 3 in the apparatus 1, and the apparatus inside was evacuated almost to a vacuum condition and, then, the samples were heated to 750-780°C by means of heaters 5. After attainment of the specified sample temperature, oxygen gas was introduced into the apparatus 1 and the CrN film on the sample surface was oxidized, and the resulting samples were used as substrates for ⁇ type-based alumina film formation.
  • ⁇ crystal structure-based alumina film was formed on the above-mentioned oxidized layer.
  • the apparatus shown in Fig. 7 as used for film formation was constituted such that the turntable 3 could be rotated and the satellite rotary members (substrate holders) 4 disposed thereon could also be rotated, so that the satellite rotary members (substrate holders) 4 could show a rotation movement while showing a revolution movement.
  • the substrates 2 were fixed to the satellite rotary members (substrate holders) 4 so as to face the sputtering cathode 6 and the rotation of the satellite rotary members (substrate holders) 4 was stopped.
  • the formation of the alumina films was carried out in an argon- and oxidizing gas-containing atmosphere by the pulsed DC sputtering method after mounting an aluminum metal target on the sputtering cathode 6 shown in Fig. 7 .
  • either one of the two sputtering cathodes 6 shown in Fig. 7 was used for film formation.
  • the film thickness and film formation time per substep in forming films intermittently were adjusted by controlling the numbers of revolution of the turntable 3 and/or of the satellite rotary members (substrate holders) 4 and/or the discharge power.
  • the discharge power given to the sputtering cathode 6 was about 3 kW, the Ar gas flow rate was maintained at a constant level of 120 sccm, and the oxygen gas flow rate and discharge voltage were adequately adjusted so that the discharge condition might be in the transition mode.
  • the composition of the gas evaporated was analyzed by a plasma emission spectrometer analyzer located at about 20 mm distant from the target surface from which aluminum atoms to be evaporated, the emission intensities of aluminum and oxygen were measured as measures and, based on the measurement results, the discharge voltage was adjusted.
  • Heating was carried out using the center heater 5 and the heaters 5 disposed on the apparatus wall surface, and the substrate temperature during film formation was maintained within the range of about 750-780°C.
  • the rotation or no rotation and the numbers of revolutions of the turntable 3 and satellite rotary members (substrate holders) 4, and the film formation time were as shown in Table 2.
  • the film thickness per substep was calculated from the thickness of the alumina film obtained, the film formation time and the revolution speed.
  • each satellite rotary member (substrate holder) 4 is rotated about once during its passage through the film forming region before each target whereas the film formation on the substrate fixed to one site of a satellite rotary member (substrate holder) 4 is carried out, for example, once or dividedly twice [film formation just after entering the film formation region and repeated film formation just before leaving the film formation region after moving to a position not facing any target as a result of the rotation of the relevant satellite rotary member (substrate holder) 4] according to the timing of the passage of the satellite rotary member through the region (film formation region) before the target.
  • the film thickness per substep becomes greatest when film formation is carried out in one stroke among the film formation carried out in one stroke, and the film formation in the first half or the latter half as divided into two. Therefore, the value of said maximum thickness is shown in Table 2 for each example.
  • the film thickness per substep was increased in Reference Example 6 by varying the revolution speed of the turntable 3 during film formation.
  • the thicknesses of the thus-formed alumina films were determined by measuring the differences in level on a silicon substrate. Further, the surface of each laminate film formed was analyzed by means of a grazing incidence X ray diffraction analyzer, and the crystal structure of the alumina film formed as the uppermost coat layer was identified.
  • Comparative Example 2 films were formed while the turntable 3 shown in Fig. 7 alone was rotated. In this case, the film formation was carried out while rotating, unlike Comparative Example 1, and, therefore, it can be confirmed that ⁇ crystal structure alumina was formed in larger proportions in the alumina films obtained as compared with Comparative Example 1. However, the film thickness obtained in each substep exceeded the upper limit specified herein and, as a result, the proportion of the ⁇ crystal structure was high.
  • ⁇ crystal structure alumina films can be formed more easily as the thickness of the film formed per substep decreases and that when the film thickness per substep is reduced to 5 nm or below as specified herein, ⁇ crystal structure-based alumina films can be formed. It is also evident that when the film thickness per substep is preferably reduced to 2 nm or below, the ⁇ crystal structure proportion can be still more increased and that when the film thickness per substep is more preferably reduced to 1 nm or below, alumina films mostly having the ⁇ crystal structure alone can be formed.
  • Reference Examples 4 and 5 are examples in which both the turntable 3 and satellite rotary members (substrate holders) 4 shown in Fig. 7 were rotated and, in Reference Example 5 , the numbers of revolutions of the turntable 3 and satellite rotary members (substrate holders) 4 were increased as compared with Reference Example 4
  • each substrate 2 is still rotating even when it arrives at a position facing the sputtering cathode 6 as a result of revolution and, therefore, the film formation time per substep becomes shorter as compared with the case of mere revolution of the substrate 2.
  • the thickness of the film formed per substep decreases and, further, the film is readily and sufficiently exposed to the oxidizing gas-containing atmosphere, so that the formation of the ⁇ crystal structure becomes easier.
  • Reference Example 6 is an example in which the turntable 3 alone in the apparatus shown in Fig. 7 was rotated. After the lapse of 60 minutes from the start of film formation, the revolution speed of the turntable 3 was decreased from 6 rpm to 3 rpm to thereby increase the thickness of the film formed per substep. Comparison with Example 1 of the invention in which the revolution speed of the turntable 3 was maintained at 3 rpm throughout the whole film formation step reveals that the formation of ⁇ crystal structure alumina films can be promoted by increasing the revolution speed in question in the early stage of film formation alone.
  • ⁇ crystal structure-based alumina films having good heat resistance can be formed efficiently without putting the substrates and apparatus, among others, under thermal load.
  • cutting tools and the like improved in wear resistance and heat resistance as compared with the prior art can be provided in the manner of mass production.
  • ⁇ crystal structure-based alumina films higher in hardness can be formed and, thus, cutting tools and the like further improved in wear resistance and heat resistance can be provided.
  • such alumina films as mentioned above can be formed efficiently in a relatively low temperature range not exceeding 800°C, in which the thermal load on the substrates, apparatus and so forth is small.

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Claims (9)

  1. Verfahren zum Herstellen eines α-Kristallstruktur-basierten Aluminiumoxidfilms, das umfasst:
    einen initialen Schritt des Bildens einer Unterbeschichtung des Aluminiumoxidfilms mit einer α-Kristallstruktur unter Bedingungen, die für die Bildung von α-Kristallstruktur-Aluminiumoxid geeignet sind, durch Sputtern eines Aluminiummetalltargets in einer oxidierenden Gasenthaltenden Atmosphäre; und
    einen nachfolgenden zweiten Schritt des Fortführens des Bildens eines Films durch Ändern der Filmbildungsbedingungen, wodurch ein α-Kristallstruktur-Aluminiumoxid weiter auf der Unterbeschichtung gebildet wird.
  2. Herstellungsverfahren nach Anspruch 1, wobei die Filmbildungsbedingungen zu Filmbildungsbedingungen höherer Geschwindigkeit für die nachfolgende Filmbildung nach der Filmbildung unter für die Bildung von α-Kristallstruktur-Aluminiumoxid geeigneten Bedingungen geändert werden.
  3. Herstellungsverfahren nach Anspruch 1, wobei die Filmbildungsbedingungen zu Bedingungen geringerer Temperatur für die nachfolgende Filmbildung nach der Filmbildung unter für die Bildung von α-Kristallstruktur-Aluminiumoxid geeigneten Bedingungen geändert werden.
  4. Herstellungsverfahren nach Anspruch 1, wobei die Filmbildung in einem frühen Stadium der Filmbildung in der Vergiftungsmodus-Entladebedingung ausgeführt wird und dann die Entladebedingung zu dem Übergangsmodus oder Metallmodus für die nachfolgende Filmbildung geändert wird.
  5. Herstellungsverfahren nach Anspruch 1, wobei die Filmbildung in einem frühen Stadium der Filmbildung bei einer Filmbildungsgeschwindigkeit, die 1 nm/min nicht übersteigt, ausgeführt wird, und dann die nachfolgende Filmbildung bei einer Filmbildungsgeschwindigkeit von nicht weniger als 3 nm/min ausgeführt wird.
  6. Herstellungsverfahren nach Anspruch 1, wobei die Filmbildung in dem frühen Stadium der Filmbildung bei einer Substrattemperatur von nicht weniger als 800°C ausgeführt wird und dann die Substrattemperatur auf 650-750°C für die nachfolgende Filmbildung abgesenkt wird.
  7. Herstellungsverfahren nach Anspruch 1, wobei die Filmbildung unter für die Bildung von α-Kristallstruktur-Aluminiumoxid geeigneten Bedingungen von einem Ändern, für die nachfolgende Filmbildung, der Filmbildungsbedingungen zu solchen, unter welchen Filme mit höherer Härte gebildet werden können, gefolgt wird.
  8. Herstellungsverfahren nach Anspruch 1, wobei die Filmbildung unter für die Bildung von α-Kristallstruktur-Aluminiumoxid geeigneten Bedingungen von der nachfolgenden Filmbildung unter Anlegen einer negativen Vorspannung, die in ihrem absoluten Wert erhöht ist, gefolgt wird.
  9. Herstellungsverfahren nach Anspruch 1, wobei die Filmbildung in einem früheren Stadium der Filmbildung ausgeführt wird, während eine negative Vorspannung von nicht höher als 100 V im absoluten Wert an die Substrate angelegt wird und dann die negative Vorspannung auf 200 V oder darüber im absoluten Wert erhöht wird und die nachfolgende Filmbildung ausgeführt wird.
EP03784599A 2002-08-09 2003-08-08 VERFAHREN ZUR HERSTELLUNG EINES ALUMINIUMOXID- ÜberzugS MIT KRISTALLSTRUKTUR VOM a-TYP ALS PRIMÄRSTRUKTUR Expired - Lifetime EP1541707B1 (de)

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